Refining of mineral oils



March 12, 1946.

G. H. CUMMINGS ETAL 5 2,396,302

REFINING OF MINERAL OILS Filed Dec. 7, 1940 1 &

t B h Patented Mar. 12, 1946 zascsoz- I OFFICE REFINING or MINERAL oILs George H. Cummings, State College, Pa., William I. Sweeney, Elizabeth, Fenske, State College, Pa., asslgnors of onehalf to Standard Oil Development Company, a corporation of Delaware, and one-half to Him dz Haas Company, a corporation of Delaware Application December I, 1940, Serial No. 369,054

. 14 Claims. The present invention relates to the refining of mineral oils and is particularly concerned with the separation and recovery of naphthenes from feed mixtures containing the same. In accord.- ance with the present process, mineral oils are treated in a manner to segregate the naphthenes, utilizing a particularly desirable solvent which comprises liquid ammonia. Tothis may be added a modifying solvent which is characterized by having the ability to change the solvent power of the ammonia. This application contains subject matter in common with. and is a continuationin-part of our application No. 353,448 filed August 21, 1940.

Within the last few years it has become apparent that petroleum and its fractions are a potential source of many desirable organic compounds. Some of. these compounds, such as arematics, naphthenes, d paramns, are present in crude unrefined petroleum oils and may be increased in concentration and amount by various operations. Other types for example, olefins and dioleflns, may be feed by subjecting certain fractions to various cracking processes and related operations. Separation processes are vital forthe production of these organic compounds, not only in the final preparation of them in a pure state, but also in the preparation of suitable feed fractions which are "to he further processed. Distillation operations have been used for the separation of various fractions oi. petroleum, but are not suited for the segregation of these constituents in a pure state due to the overlapping of boiling points 01 many of the desired constituents with other components. More recently solvent extraction operations have been employed in conjunction with distillation operations in order to secure emcient separations. In these solvent treating processes organic solvents, such as phenol, i'urfural, cresols, nitrobenzene, aniline, beta beta dichlorodlethyl ether and the like, have been employedfor the segregation of the relatively more aromatic type constituents from the relatively more paraflinic type constituents of lubricating oils. However, these organic solvents are not satisfactory for segregating constituents boiling in the lower molecular weight boiling range, particularly in the range below the boiling range of lubricating oils. Inorganic solvents, such as sulfur dioxide, sulphuric acid, and solutions containting copper and silver salts have been used for segregating constituents boiling in the lower molecular weight boiling range.

Although numerous solvents have been proposed ponent in the oil or rafllnate phase.

N. J., and Merrell R.

for separating lower molecular weight aromatic and olefin constituents from paraflin constituents, these solvents which are applicable for the selective extraction of unsaturated compounds from saturated compounds generally are not satisfactory for segregating cyclic saturated compounds, such as naphthenes, from the open chain saturated compounds or paraiiins. For example, although sulfur dioxide has a high preferential selectivity for the more unsaturated or polar constituents, such as aromatics and olefins, over the saturated constituents, such as naphthenes and paramns, its selectivity for the saturated cyclic compounds, namely, naphthenes, over the open chain saturated compounds, namely, paraflins, is so low as to make this solvent useless for efiecting separations between these two hydrocarbon classes. r

We have discovered that liquid anhydrous ammonia possesses a valuable selectivity for naphthenes over paraffins, in addition to its selectivity for the more polar over the less polar compounds. Herein resides one element of our invention. Another element is concerned with extending the solvent power. of ammonia to cover a wide range of hydrocarbons, without impairing its selectivity. as hereinafter described.

In order to secure a clear concept and value of a particular solvent, a selectivity factontermed beta, is employed. This factor is quite analogous to the alpha. factor employed in distillation and may be represented by the following formula:

in which the terms X and Y are used to denote concentrations in the raflinate and extract or solvent phases, respectively, while A and B denote, respectively, the more soluble and less soluble components or portions of the material being extracted. Through the concept of beta the limiting conditions for any separation can m determined as described by Varteressian and Fenske,

Thus, YA/YB.

Ind. Eng. Chem. 29, 270 (1937) v equals the ratio of the more soluble component to the less soluble component in the solvent or extract phase, and XA/XB equals the ratio of the more soluble component to the less soluble com- Beta is a numerical measure of the solvents selectivityor the solventfsability to preferentially dissolve one particulartype'of constituent tothe exclusion of other types of constituents.

Proper solubility of hydrocarbon in solvent is vitally important in the efficient extraction and separation of pure type compounds. The extractable component must not be completely miscible with the solvent under the conditions of extraction for otherwise this component cannot be prepai ed in a pure state. The solubility should not be too high for we have found that the selectivity or beta is closely dependent upon the solu bility and when the hydrocarbon dissolves to too great an extent in the solvent, the selectivity may be so low as to make the process uneconomlcal.

. In general, we prefer that the solubility of hydrocarbon in the solvent never exceed 35%. On the other hand, it is also important that the solubility, particularly at the hydrocarbon feed point, not be too low, for otherwise too high a solvent= to-oil ratio will be required to remove the er tractable component from the feed. We prefer that the solubility at the hydrocarbon feed point lie in the range of 5% to 3il%, particularly be tween l0% and 20%. For the most emcient extractions we have found that it is desirable to employ two extraction zones, a stripping zone where the extractable component is removed as completely as possible from the feed, and an enriching zone where the extractable component is purified from the other components which are of necessity partially dissolved, to a minor degree, in the stripping zone. Because of the different solubility characteristics of the different compo= nents, it is frequently desirable to employ diilerent dissolving capacities of the solvent in the .two zones.

From the foregoing it is apparent that proper solubility control is vital to efflcient extraction. Control by temperature is not always feasible or possible. Temperatures requiring refrigeration are undesirable as they frequently make the process uneconomical. Furthermore, we have found that the selectivity or beta of ammonia de creases at higher temperatures often to a pro hibitive degree. in some cases the components may not exist in a liquid state at the desired temperatures, in other cases the pressures may be so h h as to require special equipment.

It is known in the art to control solubility over narrow ranges by the use of modifying solvents. While well understood in principle, this method has not worked well in practice. A primary ob= jection to the use of modifying solvents is that a loss in selectivity of the solvent results. For example, the use of benzene withsulfur dioxide reduces the selectivity of this solvent to an almost prohibitive degree. Likewise. we found in one case that the use of a paraninic oil with sulfur dioxide reduced its selectivity to one-twentieth of its former value. It is often diificult to find modifying solvents which are compatible with primary solvents. For example, very few liquids may be added to furfural or beta beta dichlorocal reactivity. Few, if any, liquids soluble in aceacoe either by the use of ammonia alone or by means of closely related solvents due to the restricted solvent power oi liquid anhydrous ammonia and the low selectivity of other solvents for naphthenes over parafiins. We have discovered that ammonia is compatible with a variety of substances capable of varying its solvent power for hydrocarbons, that when these modifying solvents ror aoljustina solvent power over a definite range are used, little, if any, loss in selectivity occurs,

and that there i substantially no increase in corrosiveness or in emulsions. when amonia is modified as disclosed herein, its solvent power may be varied over a range such that naphthenes over a wide molecular weight range may be efi= ciently segregated and recovered from the correspending paramns.

Suitable modifying solvents can be chosen from a relatively large group. Any substances which will not react but which when added to the system will alter the solvent power or the ammonia may be used, specific examples of which are the higher glycols, others and ether=alcohols, methanol and other alcohols, alcohohamines, aniline, pyridine, the methylamines and other low mo lecular weight aliphatic amines to raise the sol vent power and water, ethylene glycol, lorm= amide, ethylene diamine and various parai-linic hydrocarbons to reduce the solvent power. We have found that water, ethylene glycol, the moth ylamines, the lower molecular weight diamines, and higher molecular weight para-mole hydro= carbons are especially efiective, In certain oper ill sulfur dioxide will reduce its solvent power without a chemical reaction occurring or without causing corrosion of the equipment, Water is soluble in phenol to only a limited extent and often causes emulsion and corrosion difllculties.

We have, further, discovered that the useful solvent range of ammonia for selective extraction of naphthenes from parailin may be extended 1 over a wide range of molecular weight without impairing its selectivity. We have discovered that providing the characteristics of ammonia be modified with the. desired modifying agent, it is possible to treat feed oils for the production of roducts which otherwise could not be secured atlons we find it advisable to add one tree o2 modifying solvent in one some of the extraction and another type in another zone, the resulting solvent being composed of ammonia, a modif ing solvent for increasing: the solvent power of the ammonia, and a modifying solvent tor decreasing it. lit is essential that the solvent be composed predominantly oi ammonia, present in a concentration above sea, preferably above l5%. It is not necessary that the modifying solvent be selective, it is only necessary that it increase the solvent power oi the ammonia Furthermore, it is not necessary that the modifying solvent be completely soluble in the liquid ammonia. We have found particularly that hydrocarbons which distribute themselves between the extract and ramnate phases in such a way that they appear predominantly in the ramnam phase are very emcient in lowering the solvent power of the liquid ammonia. It is to be understood that such hydrocarbons, to be added to reduce the solvent power of ammonia, will be selected so they can be separated from the hydrocarbons being extracted usually by means of distillation.

Our modifying solvents may be added directly to the ammonia, or may be added to a counter= current treating system at a plurality of points. We have found the addition of the modlfyins sol vent at one or more points in a countercurrent extraction path is particularly eflective. In this way the solubility is controlled so as always to be within the proper limits in order that the selectivity or beta is relatively high.

The ammonia and the modifying solvent may partition themselves between the extract and rafllnate phases in a diflerent concentration ratio. As a result, when counter-current treatins operations are being employed, the composition of the solvent may change along the countercurrent path. In general, this composition change will have a beneficial eflect, for the solvent usual- 1y decreases in solvent power because of this change as it flows through the countercurrent extraction path. This effect also aids in maintaining the solubility at a more constant value, and leads to more eflicient extraction.

The amount of modifying solvent added depends upon the degree to which the solvent power is to be changed, and will thus depend upon the mixture being extracted and the particular modifying solvent is used. In general, the solvent mixture should comprise above 50% ammonia, preferably above 75% ammonia.

We have found that it is possible and frequently desirable to carry out the entire extraction operation for naphthenes from parafiins at the same temperature and with the same solvent composition. In carrying out separations in this manner, a desirable operating temperature is employed such that neither refrigeration nor very high temperatures with corresponding poor selectivities are required. The amount of modifying solvent necessary is then determined which will control the solubility of the naphthenes in the ammonia in the range from about 15 to 35%, preferably in the range from about 20 to 25%.

In order to further illustrate our invention, the following examples are given which should not be construed as limiting the same in any manner whatsoever.

Example 1 Example 2 A feed mixture comprising 25% methyl naphthalene, 25% tetralin and 50% decane was extracted in a countercurrent extraction apparatus similar to Figure 1 at 100 F. with a solvent comprising 92% ammonia and 8% water. Methyl naphthalene was obtained as an extract in a purity of 98%. The ramnate was re-extracted with liquid anhydrous ammonia at 100 F. to yield a second extract comprising 98% tetralin, and a second ramnate comprising 98% decane. A solvent-to-oil ratio of :1 was employed.

Example 3 It is impossible to separate cyclopentane from neohexane by any practical distillation process. It is believed these two compounds form a constant boiling mixture. Many azeo'tropic fractional distillations also do not separate them. However, using liquid anhydrous ammonia as a solvent, a feed mixture containing 25% cyclopentane and 75% neohexane can be separated to yield cyclopentane of 95% purity by extracting in a countercurrent extraction apparatus similar to Figure 1 at a temperature of 95 F., and at a 10 to 1 solvent-to-oil ratio.

The present invention may more readily be un derstood by reference to the attached drawing illustrating a preferred modification of the same. For the purpose of illustration, it is assumed the feed comprises 30% methylcyclohexane in n- 3 heptane, and the solvent comprises 25% monomethylamine and 75% ammonia.

The hydrocarbon feed mixture is introduced by means of line 2 into extraction tower I. The

feed is introduced into the top of tower I although an intermediate feed point may have been used. By extraction tower l we mean my suitable countercurrent phase contacting device. It may be a series of mixers and settlers, a packed tower, and the like. These phase contacting paths are equipped with heating and cooling devices so that the temperature may be controlled at any desirable level or controlled to produce a temperature gradient. For this specific case it is assumed that the temperature is controlled at F. The ammonia-monomethylamine is introduced by means of line 3 into tower I. Here it contacts the down-coming oil phase and dissolves substantially all the methylcyclohexane together with minor proportions of n-heptane. The extract phase leaves tower I through line 5 and enters near the bottom of extraction tower l2. This tower is also run at a constant temperature of about 100 F., and is similar in construction to tower I. In tower l2 most of the nheptane is removed from the extract phase so that the extract phase leaving this tower at the top consists essentially of the methylcyclohexane dissolved in solvent. This extract phase is removed by means of line I4 and passed to extraction tower l5 where it contacts countercurrently a higher boiling parafiinic mineral oil which enters this tower through line IT. This oil dissolves all the hydrocarbon from the solvent so that hydrocarbon-free solvent leaves tower l5 by means of line 16 and is returned to storage tank Id. The parafilnic oil leaving the bottom of tower l5 contains all the hydrocarbons and some solvent. It is taken by means of line I!) to evaporator 20 where all the hydrocarbons and solvent are flashed ofl. The pure paraffinic oil is then returned to tower It by means of line I! while the hydrocarbon and solvent vapors are taken by means of line 2| to coil 31] in the bottom of distillation column 22. The vapors condense in this coil and furnish the necessary heat for column 22, which is run at a lower pressure than evaporator 20. The condensed vapors enter column 22 through line 29 after passing through pressure reducing valve 33. The solvent is removed overhead by means of line 24 and passed to condenser 25. Part of the solvent condensate is returned by means of line 28 as reflux to prevent any hydrocarbon from distilling over while the remainder is taken by means of line 21 to solvent storage l8. Solvent-free hydrocarbon is obtained in the still of 22 which is removed by means of line 23. Part is taken from 3i. as a final extract product while the rest is returned as reflux to extraction tower 12 by means of line 32. The hydrocarbon layer from the bottom of this tower is returned to tower I by means of line E3. The hydrocarbon layer from the bottom of tower I consists mainly of n-heptane containing a little solvent. This is taken by means of line i to distillation column 6 where the solvent is should be emphasized that an aromatic or unsaturated hydrocarbon oi approximately the same molecular weight as a naphthene is more soluble in our ammonia solvents than the naphthene. Gonsequently, it naphthenes are to be the principal or main extraction product produced by our process, the feed mixture is preferably aromaticand unsaturate-iree. Further, for ob taming naphthenes of maximum purity directly from our extraction process, we prefer to extract mixtures of a relatively narrow molecular weight range due to the efiect of molecular weight or solubility. A range oi about units in molecular weight is usually satisfactory.

In case aromatics audios unsaturates are presout along with the naphthenes, our process is particularly applicable to segregating the arcmatics and/or unsaturates from the naphthenes at the same time that the naphthenes are being segregated from the parafins, for, according to our invention, the solubility of each of these hydrocarbon types may be maintained at values to make such a separation very practical. For example, if a hydrocarbon mixture of 95 to 125 molecular weight range containing aromatics and 'olefins along with naphthenes and paraihns is to be extracted, we prefer to segregate the aromatics and olefins at the end of the enriching section using an ammonia solvent of reduced solvent power, while at the end of the stripping section a rafflnate consisting of substantially pure paraffins is withdrawn, this ramnate having been extracted in the stripping section with an ammonia solvent of enhanced dissolving power. At some point between the above-mentioned extract and rafiinate ends of this primary extraction system, the naphthenes will be concentrated. A point is selected in this primary extraction path where the naphthenes are freed of either the paramns or the aromatics and olefins. At least part of one of the phases is then withdrawn, and further extracted in a secondary extraction system with an aonia solvent of the correct dissolving power to free the naphthenes of the other remaining components. The phase from the secondary extraction system containing substantially pure naphthenes is then withdrawn and heated to recover the naphthenes from the solvent, while the other secondary extraction phase is returned to the primary extraction path at a point near the original withdrawal point.

A process, such as the one above described, is known as side-stream withdrawal. This is a particularly desirable method of processing when using aonia solvents with a multi-component feed xture.

It is obvious that if paramns were not present in the feed mixture, then the naphthenes could be separated Zrom the aromatics and unsaturated constituents as a primary ramnate in the ammonia extraction process herein described. 7

These ammonia solvents are also applicable to the segregation of naphthenic-type hydrocarbons from relatively narrow fractions having molecular weights up to about 500. In these instances, the material is preferably free of more polar hydrocarbon types such as aromatics and unsaturates. Also, modifying solvents to increase the solvent power are usually required in extracting these higher molecular weight fractions. Methylamine is a. particularly desirable modifying solvent in these instances. Naphthenic-type hydrocarbons in these higher molecular weight mate- Ms are usually classified and recognized by one aseaaoa or more oi rollowing features: is) releatlvely low your points with res ect to the o finic invdrocarbons or" similar molecular (b) an intermediate value of viscosit ranging, for example, from. about 5d t" for hydrocarbons otherwise aroma value of aniline point intermerhaw matics and psrafins, example, b and to) values oi index, aniline and molecular according to m thod of Wate characterized Ammonia inorganic solve operated from the .Yeed oil and which may l c also separated from the modifying agent. Ammonia is an inorganic solvent which together with a satisfactory modifying agent as disclosed in the present application will eihciently and economi-= cally separate complex naphthene organic sub stances from hydrocarbon oils.

The following definitions relate to the claims and the preceding specification.

By a predominate proportion of liquid ammonia we mean liquid aonia together with modifying solvent such that the ammonia contributes principally to the solvents selectivity, as illustrated in the preceding examples.

onia solvent means liquid ammonia together with any modifying solvent.

By a modifying solvent we mean any liquid which when added to the system will alter the solvent power oi the solvent. The modifying solvent may or may not be-a selective solvent, its determining characteristic being only that it will change the dissolving capacity of the liquid ammonia.

The term zone denotes one or more extraction stages or the equivalent which are properly interconnected, as already demonstrated, wherein continuity of flow and control of operating variables are maintained. By a first zone we mean that portion of the extraction path between which the feed oil enters and the rafinate phase leaves the system. By a second zone we mean an extraction path along the line of solvent flow beyond the point of feed oil introduction.

Extracting a feed mixture means extracting the mixture in a first zone. t may also include the extraction or the more soluble components of the feed in a second extraction zone.

Relatively high dissolving capacity means the ammonia solvent dissolves the extractable component or components to a considerable degree if not completely, and such a solvent is capable of dissolving appreciably the raihnate portions or components. Relatively low dissolving capacity means the ammonia solvent is incompletely miscible with the extractable component or components, and the solubility of such materials in the solvent is usually 20 to 30% o lower, While the. ramnate portions or components are relatively insoluble, i. e., the solubility of such material is of the order of 3 to 10% or less.

By mineral oil we mean mixtures that are predominantly hydrocarbons, such as exist in petroleum or its fractions, or predominantly hydrocarbon mixtures obtalned by processing such fractions.

By naphthene we mean substances thatcontain a relatively aturated cyclic hydrocarbon struc ture. For the most part the cyclic structure is composed of methylene or substituted methylene groups such as in cyclopentane and methylcyclohexane, as herein illustrated. However, there may be ome unsaturation such as in cyclohexane. Also, there may be variou other hydrocarbon groups, such as p'arafiinic or olefinic radicals, attached to these naphthenic structures.

The term methylamine is used to denote mono-, di-, o trimethylamine, or mixtures of these. 4

The present invention is not to be limited by any theory or mode of operation but only in and by the following claims in which it is desired to claim all novelty insofar as the prior art permits.

We claim:

1. A process for the segregation of naphthenes with an average molecular weight less than about 250 from a feed mixture consisting of naphthenes and paraifins, the constituents of which boil over a relatively narrow boiling range, which comprises treating said feed mixture with a olvent comprising liquid ammonia under conditions to form a solvent extract phase containing naphthenes and relatively free of paraifins, and a raffinate phase containing paraffins and relatively free of naphthenes, separating the solvent phase containing naphthenes, and recovering solvent and naphthenes therefrom.

2. A process for the segregation of naphthenes with an average molecular weight less than about 250 from a feed mixture consisting of naphthenes and paraffins, the constituents of which boil over a relatively narrow boiling range, which comprises treating said feed mixture under conditions to form a solvent extract phase containing naphthenes and relatively free of paraifins, and a rafiinate phase containing parafiins and relatively free of naphthenes, with a solvent comprising ammonia to which a liquid modifying solvent having the ability to increase the solvent power of the ammonia is added in at least a part of the extraction path, separating the phase containing naphthenes, and recovering solvent and naphthenes therefrom. i

3. A process for the segregation of naphthenes with an average molecular weightless than about 250 from a feed mixture consisting of naphthenes and parafiins, the constituents of which boil over a relatively narrow boiling range, which comprises treating said feed mixture under conditions to form a solvent phase containing naphthenes relatively free of parafiins, and a rafiinate phase containing paraffins and relatively free of naphthenes, with a solvent comprising liquid ammonia to which methylamine is added in at least a part of the extraction path, eparating the phase containing naphthenes, and recovering solvent and naphthenes therefrom.

4-. A process for the segregation of naphthenes with an average molecular weight less than about 5. A process for the segregation of naphthenes with an average molecular weight less than about 250 from a feed mixture of naphthenes and parafiins, which comprises treating said feed mixture under conditions to form a solvent xtract phase containing naphthenes and relatively free of paraffins. and a raflinate phase containing parafiins and relatively free of naphthenes, with a solvent comprising a major proportion of liquid ammonia to which is-added in at least a part of t the extraction path a minor proportion of water,

separating the solvent phase containing naphthenes, and recovering solvent therefrom.

6. A process for the segregation of naphthenes with an average molecular weight less than about 250 from a feed mixture of naphthenes and Paraffins, which comprises treating said feed mixtures with a solvent comprising ammonia and a liquid and naphthenes modifying solvent which is characterized by havering solvent and naphthenes therefrom.

7. A process as defined by claim 6 in which said solvent having the ability to increase the solvent 250 from a feed mixture of naphthenes and paraffins, the constituents of which boil over a relatively narrow boiling range, which comprises treating said feed mixture under conditions to form a solvent extract phase containing naphpower of ammonia is methylamine, and in which the substance having the ability to decrease the solvent power is water.

8. A process as defined by claim 6 in which said solvent having the ability to increase the solvent power of ammonia is methylamine, and in which the substance having the ability to decrease the solvent power comprises a hydrocarbon slightly soluble in the extract phase but completely soluble in the rafiinate phase.

9.- A process for the segregation of naphthenes with an average molecular weight less than about 250 from a feed mixture of naphthenes and paraflins, which comprises treating said feed mixture under conditions to form a solvent extract phase containing naphthenes and relatively free of paraifins, and a rafiinate phase containing parafiins and relatively free of naphthenes with a solvent comprising liquid ammonia and to which is added in at least a part of the extraction path afterthe feed mixture has contacted the liquid ammonia a hydrocarbon slightly soluble in the extract phase but completely soluble in the ratfinate phase, separating the solvent phase containing naphthenes, and recovering solvent and,

naphthenes therefrom.

10. A process for the segregation of naphthenes with an average molecular weight less than about 250 from a feed mixture consisting of naphthenes and parafiins, which comprises extracting said mixture at temperatures in the range of 70 F. to F. with ammonia solvent under conditions that there are formed a solvent extract phase containing naphthenes and relatively free of paramns, and a rafiinate phase containing paraifins and relatively free of naphthenes, separating the solvent phase containing naphthenes, and recovering naphthenes and solvent therefrom 11. A process for the segregation of naphthenes with an average molecular weight less than about 250 from a feed mixture containin:

the same together with parafcli s which som prises extracting said iced mix a countereurrent treating path comprising a stripping zone and an enriching zone with a solvent comprising liquici ammonia, separating at ieast a part of one of the phases at such an intermediate ZCSOint in the extraction path that separated phase is relatively free of narafiins contains primarily naphthenes and components of ar i solubility than the naphthenes together wi" solvent, and further extracting saici separated. phase with a solvent comprising a major proportion of iiquici ammonia together with a soivent to reduce the solvent power of the ammonia for naphthenes in order to purify the naphthenes.

12. A process for the segregation of naphthenes with an average molecular Weight iess than about 250 from a feed mixture containing the same together with paramns and components which are more soluble in the solvent than the naphthenes, which comprises extracting said feed mixture in a countercurrent treating path. comprising a stripping zone and an enriching zone with a solvent comprising liquid ammonia, separating at feast a part of one of the phases at such an intermediate point in the extraction path that the separated phase consists primarily of naphthenes and parefins together with solvent, and further extract ing said separated phase with a solvent comprising liquid ammonia to separate the naphthencs from the paraffim.

13. A process for the segregation of methylcyclohexane from paraffins which comprises extracting the said mixture at temperatures in the range of 70 F. to 120 with a solvent comprising ammonia containing from 10 to 36 per cent methylamine.

M. .42 process for the segregation of cyciopentane from parafiins of similar boiiing point, which comprises extracting the said mixture with liquid ammonia at temperatures in the range of 79 2 to 120 F.

GEORGE H. CUMIWINGS. W'ILEZAM J. SWEEIJEY. MERRELL R. FENSKE. 

